CN1958301A - A method of patterning molecules on a substrate using a micro-contact printing process - Google Patents
A method of patterning molecules on a substrate using a micro-contact printing process Download PDFInfo
- Publication number
- CN1958301A CN1958301A CNA2006101436051A CN200610143605A CN1958301A CN 1958301 A CN1958301 A CN 1958301A CN A2006101436051 A CNA2006101436051 A CN A2006101436051A CN 200610143605 A CN200610143605 A CN 200610143605A CN 1958301 A CN1958301 A CN 1958301A
- Authority
- CN
- China
- Prior art keywords
- molecule
- solvent
- base material
- patterned surface
- patterning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/006—Patterns of chemical products used for a specific purpose, e.g. pesticides, perfumes, adhesive patterns; use of microencapsulated material; Printing on smoking articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C1/00—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating
- B05C1/02—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating for applying liquid or other fluent material to separate articles
- B05C1/027—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating for applying liquid or other fluent material to separate articles only at particular parts of the articles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00206—Processes for functionalising a surface, e.g. provide the surface with specific mechanical, chemical or biological properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00351—Means for dispensing and evacuation of reagents
- B01J2219/00382—Stamping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00277—Apparatus
- B01J2219/00497—Features relating to the solid phase supports
- B01J2219/00527—Sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
- B01J2219/0061—The surface being organic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
- B01J2219/00612—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports the surface being inorganic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
- B01J2219/00623—Immobilisation or binding
- B01J2219/00626—Covalent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
- B01J2219/00623—Immobilisation or binding
- B01J2219/0063—Other, e.g. van der Waals forces, hydrogen bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00605—Making arrays on substantially continuous surfaces the compounds being directly bound or immobilised to solid supports
- B01J2219/00632—Introduction of reactive groups to the surface
- B01J2219/00637—Introduction of reactive groups to the surface by coating it with another layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00583—Features relative to the processes being carried out
- B01J2219/00603—Making arrays on substantially continuous surfaces
- B01J2219/00659—Two-dimensional arrays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00274—Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
- B01J2219/00718—Type of compounds synthesised
- B01J2219/0072—Organic compounds
- B01J2219/00725—Peptides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/02—Burettes; Pipettes
- B01L3/0241—Drop counters; Drop formers
- B01L3/0258—Drop counters; Drop formers using stamps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/788—Of specified organic or carbon-based composition
- Y10S977/789—Of specified organic or carbon-based composition in array format
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/788—Of specified organic or carbon-based composition
- Y10S977/789—Of specified organic or carbon-based composition in array format
- Y10S977/79—Of specified organic or carbon-based composition in array format with heterogeneous nanostructures
- Y10S977/791—Molecular array
- Y10S977/793—Protein array
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/84—Manufacture, treatment, or detection of nanostructure
- Y10S977/887—Nanoimprint lithography, i.e. nanostamp
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24917—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including metal layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
- Y10T428/24926—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer
Abstract
The present invention relates to a method of patterning molecules on a substrate using a micro-contact printing process, to a substrate produced by said method and to uses of said substrate. It also relates to a device for performing the method according to the present invention.
Description
Technical field
The base material that the present invention relates to utilize the method for micro-contact printing process patterning molecule on base material, makes by described method and the application of described base material.Also relate to the equipment that is used to carry out the method according to this invention.
Background technology
In the past decade, soft lithography has developed into and has been used for the common processes [1,2] that chemical method is made micro-structural and nano-architecture surface.In several technologies that are collectively referred to as soft lithography, micro-contact printing (μ CP) has become the most frequently used method [1].Patterned polymer die (stamp) adopts contact ink supply or wet ink supply to be covered by molecular ink.In the contact ink supply, solvent is reduced to dry state, and the molecule self assembly is on ink pad (ink-pad) simultaneously.By making die and ink pad that conformal contact the (conformal contact) be taken place, molecule is transferred on the die under environmental condition.In wet ink supply method, ink is poured on die, flows down at nitrogen then and is reduced to dry state.Under above-mentioned two kinds of situations, molecule all was positioned on the die before being transferred on the base material.For with ink transfer to base material, make die and base material that conformal the contact be taken place, to finish the transfer [3,4] of molecule from being impressed onto base material.
Recently, protein also is transferred to [5-7] on the various base materials.Therefore, the advantage of μ CP be protein directly, fast and mild the transfer, but, all μ CP technology of report finally all can cause the sex change of the protein that prints at present.The native protein that is fixed on the modified surface is most important for sensor technology, cell cultivation and microbiology.An application is the patterning [8] that for example is used for the growth factor protein matter of cell guiding growth on silica.
From the teeth outwards fixing biological molecules for example the key issue of protein, nucleic acid or the like be their sex change and loss of function after it is fixing thus.Described function for example for cytochrome c (cyt c), may depend on the orientation and the conformation of proteins on surfaces.Up to the present, at Au surface of chemical modification [9-11] and ITO[12] on studied the fixing and redox active of cyt c.People such as Runge have reported cyt c molecular transfer to the lip-deep method of ITO, wherein protein be dried on die [12].For the ITO surface, the susceptible of proof activity of proteins depends on the surface modification [11] of the die that is used for described method.
Except transferring protein, people such as Nakao have also described the method [13] of using the height-oriented DNA nano wire of PDMS die transfer printing.Fluid dynamic is used to be orientated DNA on PDMS in the method.After orientation step, make PDMS die and mica sheet that conformal the contact so that DNA is transferred on the mica be taken place.Afm image shows the apparent height of DNA of transfer like this between 0.27nm and 0.35nm, and this shows because hydrokinetic dna molecular as a result may be elongated and may be subjected to shearing.
But the above-mentioned ink supply method of all that use in the prior art all can cause protein denaturation and lose its activity.
Summary of the invention
Therefore, the object of the present invention is to provide the method for a kind of permission fixing and patterning molecule on substrate, thereby make desirable patternization and fixing molecule keep its function and/or native conformation and/or activity.In addition, the present invention also aims to provide a kind of even to the also simple patterning molecule on substrate of large biological molecule and keep the method for its function simultaneously.In addition, the present invention also aims to be provided at the method for patterning molecule on the substrate, can obtain whereby≤pattern characteristics of 200nm.
All these purposes can reach by a kind of method of micro-contact printing process patterning molecule on substrate of utilizing, and by this method the molecule of desirable patternization are maintained in the solvent or by solvent and cover.
This molecule that makes desirable patternization in whole technical process all is maintained in the solvent or also is known as " original place print process " or " original place stamped method " by the micro-contact printing process that solvent covers in this article sometimes.Term " original place print process " or " original place stamped method " in this article refer to the molecule that makes desirable patternization because the result who all is maintained in whole typography process in the solvent or is covered by solvent and can keep the micro-contact-printing of its function and/or conformation.
In a preferred embodiment, described " original place print process " is meant that the molecule that makes desirable patternization in its whole process all is maintained at the micro-contact-printing that makes under its its physiological condition separately that can keep its natural function and/or conformation.Should emphasize that term " physiological condition " will depend on the type of the molecule that will be patterned.For example, if the molecule of patterning is the oxygen transport protein molecular, will preferably include the pH value of 7.0-7.8 for a kind of like this molecule " physiological condition ", preferably at pH about 7.4.On the other hand, if the molecule of patterning is a gastric enzyme, will comprise the pH value of 1.8-4 for a kind of like this molecule " physiological condition ".Therefore, generally speaking term " physiological condition " will comprise the pH value that can be 1-10.
In one embodiment, described micro-contact-printing does not comprise drying steps.
In one embodiment, the method according to this invention may further comprise the steps:
A) be provided in the solvent will patterning molecule and the surface of patterning is provided, the surface of die form preferably,
B) when described molecule being remained in the described solvent or being covered, the molecular transfer of described desirable patternization is fixed thereon to the surface of described patterning and with them by described solvent,
C) provide base material and make the surface of described patterning conformal the contact be taken place with described base material with described molecule fixed thereon, on described base material, set up the pattern of described molecule thus, described molecule is remained in the described solvent or by described solvent cover.
The conformal contact " taken place with so-and-so " and is meant for example contact between the surface of two entities in term, and it allows to shift to another entity at the molecule of contact anteposition on one of them entity.In certain embodiments, realize that described transfer need exert pressure, and in this case, the conformal contact " taken place with so-and-so " and will be equal to " being pressed in so-and-so goes up " in term.
Term " molecule is fixing from the teeth outwards " in this article refers to and makes molecular change must be attached to lip-deep behavior, is not meant that fixing thus molecule will can not move fully.For example, some part of fixing thus molecule will still can and/or can cover within this surperficial solvent " waving " around some chemical bond rotation." fixing " only represents that in this article molecule adheres to certain of surface, and this energy of attachment prevents that molecule from freely spreading from described surface.The simplest form of expression is molecule this fixing may the generation by described surface is exposed to described molecule from the teeth outwards.
In one embodiment, in step a), in described solvent, provide described molecule also at first to be fixed on the ink pad that is preferably non-patterned surface form that is positioned within the described solvent, wherein, preferably, described ink pad with the described molecule that is fixed thereon and described patterned surface are being contained in first solvent environment with the molecule of described desirable patternization conformal the contact taken place, described solvent and randomly buffer thus described molecular transfer is fixed thereon to the surface of described patterning and with them, and wherein more preferably, in step c), containing described solvent and randomly providing described base material in second solvent environment of buffer, and the described patterned surface that wherein has a described molecule that is fixed thereon is transferred to after step b) in described second solvent environment and with described base material conformal the contact taken place.First, second and subsequently solvent environment contain solvent and can in addition also contain solute, and as salt, the preferably buffered agent more preferably can be set up physiological condition by its existence or set up the buffer of the condition of imitation physiological status.Second and solvent environment subsequently do not comprise or only comprise the molecule that will be patterned of minute quantity at first.But, in case patterned surface or ink pad transferred to described second, third, in the fourth class solvent environment, just will have the molecule of some desirable patternization to be present in the described solvent environment.
Any surface of the promotion transitional surface of the molecule that can serve as desirable patternization represented in this article in term " ink pad ".Its simplest form can only be the surface of non-patterning.But, under certain conditions, it has pattern above also can being, and/or can absorb the molecule of desirable patternization and can discharge certain surfaces of some these molecules when die with described ink pad conformal the contact is taken place.
In one embodiment, in step b), the described ink pad that will have the described molecule that is fixed thereon transfer to contain described solvent and randomly in second solvent environment of buffer after, make described ink pad conformal the contact be taken place in described second solvent environment with described patterned surface with the described molecule that is fixed thereon, thereby described molecular transfer is fixed thereon to the surface of described patterning and with them, wherein preferably, in step c), containing described solvent and randomly providing described base material in the 3rd solvent environment of buffer, and the described patterned surface that wherein has a described molecule that is fixed thereon is transferred to after step b) in described the 3rd solvent environment and with described base material conformal the contact taken place.
In one embodiment, in step a), described molecule is provided in described solvent, and in step b), within the described solvent described molecule is being fixed on the described patterned surface, wherein preferably, step b) takes place by described patterned surface is immersed in the described solvent, and wherein more preferably, in step c), containing described solvent and randomly providing described base material in the 4th solvent environment of buffer, and the described patterned surface that wherein has a described molecule that is fixed thereon is transferred to after step b) in described the 4th solvent environment and with described base material conformal the contact taken place.
In one embodiment, need not solvent environment and described base material is provided in step c), and wherein when keeping described molecule to be covered, make described patterned surface conformal the contact be taken place with described base material with the described molecule that is fixed thereon by described solvent, and wherein contain described solvent and randomly in the 5th solvent environment of buffer being transferred to described patterned surface when described base material contacts, the transfer of described patterned surface and described base material described patterned surface with take place immediately after described base material takes place by conformal the contact, dry on described base material to avoid described patterned surface.
In one embodiment, described step b) was carried out in 1 second-60 minutes time period.Step b) can be regarded as " ink supply step ".
Preferably, make in the step c) described patterned surface and described base material conformal contact the molecule that occurs in described desirable patternization be fixed on the described patterned surface after no longer than 180min, preferably no longer than 120min, more preferably no longer than 10min, most preferably in the time period no longer than 1min.
In this article, " occur in fixing ... afterwards no longer than ... a period of time in " be meant that described making carry out conformal contact and must carry out in the time of the longest 180min, the described time period is when the molecule of described desirable patternization is fixed on the described patterned surface.
In one embodiment, after step c), described patterned surface is mentioned from described base material, thereby stay the base material of the pattern that has described molecule on it, wherein preferably, the described base material that has the molecule pattern on it is maintained in the solvent that randomly contains buffer or by its covering.
In one embodiment, the described molecule that be patterned is selected from protein, nucleic acid, preferably DNA or RNA, and lipid, and the combination of above-mentioned substance, wherein preferably, the described molecule that be patterned is a protein molecule.
Preferably, owing to all being maintained in the solvent or by solvent, the molecule in desirable patternization described in the whole micro-contact printing process process covers, so they all keep its function and/or activity and/or native conformation in whole technical process, wherein more preferably, the molecule of described desirable patternization all is maintained in whole micro-contact printing process process under the physiological condition of being measured by for example pH and salinity.
Term " solute " is not got rid of solute and is present in the solvent in this article.In fact, these may be preferred for the physiological condition of setting up expectation.These solutes include but not limited to salt and ion component, buffer, protein, nucleic acid and lipid.
In one embodiment, if the molecule of described desirable patternization is hydrophilic then described base material possess hydrophilic property surface,, the molecule of described desirable patternization has hydrophobic surface if being hydrophobic then described base material.
Preferably, described base material has the separation layer and/or the adhesive layer that can promote that described base material combines with the molecule of described desirable patternization by covalent bond, electrostatic force, Van der Waals force, hydrogen bond, London forces or their any combination.
In one embodiment, described base material is selected from metal and semimetal, monocrystalline or polycrystalline material; Preferred monocrystalline or polycrystalline metal and semimetal (most preferably gold, platinum, silicon) or composite, preferably monocrystalline or polycrystalline composite materials (silica most preferably, GaAs) or amorphous state composite (most preferably glass); Plastics, preferred elastomer (most preferably dimethyl silicone polymer), preferred plastic body (most preferably polyolefin), preferred ion polymer, preferred resist (resist) material (most preferably UV-NIL resist); With molecular layer, preferably use SAM (self assembled monolayer) modification with direct combination or indirect any above-mentioned material of combination, the SAM that is used for indirect combination will have one or more chemicals or handle to realize the binding site of expectation; The SAM that most preferably has two end groups: one is used for molecule attached to base material, as is used for the mercaptan headgroup of combination on gold; The SAM that most preferably has the silane headgroup end group that is used to be combined on the silica; Second end group is used for the coupling ink, for example have the sulfydryl or the amino SAM that are used in conjunction with metal, SAM with the carboxyl that is used for the static combination, most preferably have the sulfydryl that is used in conjunction with metal, have band be used for the interactional methylene of Van der Waals level and smooth alkane chain, have be used for covalently bound-COOH ,-SAM of OH or vinyl; Or have the SAM that is used in conjunction with the antibody of corresponding antigens, or have the SAM that is used in conjunction with the antigen of corresponding antibodies, or have the SAM of the acceptor that is used for the specific bond molecule; And have be used in conjunction with the molecular layer modification of the antibody of corresponding antigens or with have be used in conjunction with the molecular layer modification of the antigen of corresponding antibodies or with any above-mentioned material of the molecular layer modification that has the acceptor that is used for the specific bond molecule; Most preferably use the gold of sulfydryl hendecanoic acid layer (MUA) modification.
Preferably, described patterned surface is made by being selected from following material: monocrystalline and polycrystalline material such as silicon, silica, the silica on laminar composite system such as the silicon, the metal level on the silicon/oxidative silicon; Amorphous material such as glass; Plastics, as elastomer, preferred dimethione, plastic body, preferred polyolefm (POP, polyolefin plastomers), ionomer, anticorrosive additive material such as UV-NIL resist.
In one embodiment, make by being selected from following material on described ink pad surface: monocrystalline and polycrystalline material such as silicon, silica, the silica on laminar composite system such as the silicon, the metal level on the silicon/oxidative silicon; Amorphous material such as glass; Plastics, as elastomer, preferred dimethione, plastic body, preferred polyolefm (POP, polyolefin plastomers), ionomer, anticorrosive additive material such as UV-NIL resist.
Preferably, the molecule of described desirable patternization is selected from protein molecule such as redox protein matter, nucleic acid binding protein matter, enzyme, metalloprotein such as cytochrome c, azurin, cytoskeleton protein, antibody, nucleic acid such as DNA, RNA, PNA, lipid such as phosphatide and sphingolipid.
In one embodiment, the molecule of described desirable patternization is the protein molecule with one or several lysine residue, and wherein said base material is a gold, preferably have separation layer in its surface to avoid the sex change of described protein, the thickness of described separation layer is preferably within the scope of 0.5nm-200nm.
In one embodiment, pattern comprise length for about 10nm to 500 μ m, preferably about 10nm arrives≤200nm, more preferably about 10nm arrives≤feature of 150nm.Obviously, the size of the actual characteristic by the method according to this invention printing depends on that the expection of the pattern of printing is used thus.For example, if expection is applied in nucleic acid chip or sensor application field, then the average-size of print characteristics may be at 1 μ m within the scope of 500 μ m.If expection is applied in field of molecular electronics, then the average-size of print characteristics may be in about 10 nanometers to≤200nm, preferably about 10nm arrives≤scope of 150nm within.
Purpose of the present invention also can be by being reached by base material made according to the method for the present invention and that comprise the pattern of the molecule that can keep its function and/or activity and/or native conformation thereon.
Purpose of the present invention can also reach by use base material according to the present invention in sensor, bioreactor or when cell guiding is grown.
Purpose of the present invention also can reach by a kind of equipment that is used to carry out according to the inventive method, and this equipment comprises:
-hold desirable patternization molecule solution first the device,
The surface of-patterning, die form preferably,
-base material is maintained in the solvent or by solvent and covers,
-be used for that the molecule of described desirable patternization is transferred to second of described patterned surface from described first device to install,
-be used for the molecule of described desirable patternization is transferred to the 3rd device of described base material from described patterned surface,
-the molecule that is used for guaranteeing described desirable patternization is being transferred to the 4th device that described patterned surface is maintained at the solvent or is covered by solvent to the process of described base material again from described first device.
In the preferred embodiment according to equipment of the present invention, second device is an ink pad, the preferred not surface of patterning.
The unexpected discovery of inventor can utilize molecule, preferably large biological molecule such as protein, nucleic acid and/or lipid and remain at these large biological molecules in the solution or solvent (preferably aqueous solvent) under carry out micro-contact printing process.Further listed various schemes were carried out below the method according to this invention can adopt.
Here term " molecule " is meant any molecule that can have biological correlation.It comprises the nucleic acid of oligonucleotide, comprises the protein of peptide, and lipid.Described molecule can be that what to synthesize also can be natural.Concerning protein or nucleic acid, they can have naturally occurring sequence or artificial sequence.
Therefore the present inventor has described and a kind ofly can prevent for example original place imprint process of protein drying or sex change on die of after ink supply step molecule.In this μ CP technology, die, ink pad (if any) and base material all are maintained at solvent environment for example in the cushioning liquid or be cushioned solution at least and cover in all processing steps.Can under the physiological condition of original place, carry out in steps thus.
On the one hand, method of the present invention can be described by the following various technologies that further specify:
Technology 1 (referring to the scheme 1 of Fig. 4):
Ink pad is immersed in the solution of desired molecule.After several hours, even contact a few minutes with this ink pad at same container neutrality die.Then die is transferred to rapidly in the container that fills pure cushioning liquid, made that the surface of die is not dry.Contain in this cushioning liquid the base material of molecular transfer on it.Make die contact a few minutes with base material.At last the base material of modification is inserted in the cushioning liquid that does not contain the molecule that will print/impress and preserve.
Technology 2 (referring to the scheme 2 of Fig. 4):
Ink pad is immersed in the solution of desired molecule.After several hours, ink pad is transferred to rapidly in the container that fills pure cushioning liquid, made that the surface of ink pad is not dry.Make die contact a few minutes immediately with ink pad.Then die is transferred to rapidly in another container that fills pure cushioning liquid, contained target substrate in this container.Die is pressed a few minutes on base material.At last the base material of modification is inserted in the cushioning liquid that does not contain the molecule that will print/impress and preserve.
Technology 3 (referring to scheme 3):
Die is immersed in the solution of desired molecule.Molecular Adsorption is to stamp surfaces.After several hours, die is transferred to rapidly in the container that fills pure cushioning liquid, made that the surface of die is not dry.Contain in this cushioning liquid the base material of molecular transfer on it.Make die contact a few minutes with base material.At last the base material of modification is inserted in the no protein buffer solution that does not contain the molecule that will print/impress and preserve.
Technology 4 (referring to scheme 4):
The die of the scheme 1,2 of having fixed the molecule that will be stamped on it or 3 after being taken out from ink solution, it is contacted under environmental condition with base material immediately.This must be to finish under the condition that wets at die.Die and the base material that adheres to are put into the container that fills pure cushioning liquid immediately.Shift after a few minutes and finish.At last the base material of modification is inserted in the cushioning liquid that does not contain the molecule that will print/impress and preserve.
Hereinafter, describe with reference to accompanying drawing:
Description of drawings
Fig. 1: the SEM image of cyt c on (MUA)/gold.Institute's timberline be 1 μ m to 150nm, and between have equidistant from distance.Concealed wire is a cyt c molecule.
Fig. 2: the cyclic voltammetry curve (sweep speed: 5OmV/s of cyt c on the MUA/ gold; Reference electrode: SCE).The reference base material of the cyt c (▲) that do not contain cyt c (-), from solution, adsorbs, the cyt c (■) after the original place impresses or prints and the cyt c () after environment impression or printing.
Fig. 3: the cyclic voltammetry curve (sweep speed: 5OmV/s of cyt c on the MUA/ gold; Reference electrode: SCE).Compared die at the different time that in buffer container, keeps before the contact substrate, i.e. 5s (■), 10min (▲) and 2h (-).
Fig. 4: the schematic diagram that has shown different specific embodiments 1-4 of the present invention.
The specific embodiment
More particularly, Fig. 4 and shown in scheme can be summarized as follows:
Scheme 1:
The schematic diagram of original place micro-contact printing process.Ink pad is put into cytochrome c cushioning liquid 2h.Die is placed 2min on ink pad.Die taken out and drying-free and contacting rapidly with cushioning liquid.Be dipped into the auri material that basic hendecanoic acid SAM covers of being dredged of cushioning liquid.The conformal 2min of contact of die and base material is broken away from then.
Scheme 2:
The schematic diagram of original place micro-contact printing process.The ink pad immersion is contained in the solution of desired molecule.After several hours ink pad is transferred to rapidly in the container that fills cushioning liquid.Make die contact a few minutes immediately with ink pad.Subsequently die is transferred in the container that fills cushioning liquid, also contained target substrate in this container.Die is pressed in a few minutes break away from subsequently on the base material.
Scheme 3:
The schematic diagram of original place micro-contact printing process.Die is immersed in the solution of desired molecule.Molecular Adsorption is to stamp surfaces.After several hours die is transferred to rapidly in the container that fills pure cushioning liquid, contained target substrate in this container.Make that die and base material are conformal to contact a few minutes, break away from subsequently.
Scheme 4:
Wet die according to scheme 1,2 or 3 preparations after being taken out from ink solution, it is come in contact under environmental condition with base material immediately.Die and the base material that adheres to are immersed in the container that fills pure cushioning liquid immediately.After a few minutes die and base material are broken away from.
In addition, with reference to following examples, they only are used for explanation and are not used in restriction the present invention.
Embodiment
A) die and function/structural research
The molecule of desirable patternization is depended in the selection that it will be apparent to those skilled in the art that base material and die.For example it will be apparent to those skilled in the art that if print nucleic acid, then hydrophily and hydrophobic base material are fit to.According to the hydrophily of base material, DNA can fix with the form (hydrophobic surface) of bundle or with independent thigh (hydrophilic base).Those skilled in the art are also clear, the protein transduction that contains the cysteine group be moved on to gold and go up and must cover exposed gold surface by use separation layer (for example sulfydryl SAM), make protein denaturation on the gold in order to avoid cysteine is attached to.Those skilled in the art are also clear on the other hand, and hydrophilic polypeptide (having uncertain tertiary carbon and quaternary carbon structure) can be printed on the hydrophilic silicon oxide surface as the many cells lysin.Those skilled in the art are also clear, and pattern dimension is depended in the selection of moulage.The minimum pattern size depends on the stretch modulus of material strongly, and for example stretch modulus is that the dimethyl silicone polymer of 1MPa is suitable for printing the pattern up to 300nm, and for the pattern less than 300nm, stretch modulus is that the polyolefin of 1GPa may be suitable for.Those skilled in the art are also clear, printed patterns in large area, the flexible die made from flexible plastic-type material than with any other material manufacturing all more preferably because flexible die can all produce conformal contact on whole area.Those skilled in the art are also clear, and the solubility of the hydrophily of die and base material and the biomolecule that will shift is determining the interaction of this biomolecule and ink pad, die and base material.
The die that is used for this technology is made by elastomer, plastic body, ionomer, anticorrosive additive material usually, also can be made by hard material such as crystal and polycrystalline material.Also can use the combination of these materials to make composite impression (soft-soft, soft-hard and hard-hard).Die is made by master (master) with hot or light-initiated curing or by hot press printing technology by dripping casting, wherein described as required master is with release layer for example (1,1,2,2-13 fluoro-octyl groups)-the individual layer passivation of trichlorosilane or SDS (SDS).Can be by stamp surfaces being exposed to for example oxygen plasma or chemical modification being carried out on the surface of stamp surfaces by making its chemically reactive.
For following further disclosed specific embodiments, used POP (polyolefin plastomers) (Affinity VP 8770G) from Dow Chemicals.POP is heated to 85 ℃ and be pressed in silica (Sioxide) master of usefulness (1,1,2,2 ,-ten three fluoro-octyl groups)-trichlorosilane (Sigma Aldrich) passivation with the pressure of 90kPa.
All specific embodiments all use horse core cell pigment c to carry out as model system.
The redox active of protein is studied in use by PAR Model 283 potentiostats of the PC control of 2.4 editions CorrWare softwares of operation.Working electrode is a diameter 3, the gold of 5mm (l11) single-wafer cylinder.For measuring, used suspension meniscus (hanging meniscus) method.In the method, the special metal face and the electrolyte of monocrystal are come in contact by forming bent moon.The Au crystal is cleaned in sulfuric acid.After the flame annealing gold (l11) crystal is put into (Sigma-Aldrich) 10min of thin basic undecanoic acid (MUA), use ethanol and MilliQ water (18.2M Ω, carbon total amount 3-4ppm) flushing subsequently.Use standard calomel electrode (SCE) electrode for referencial use; Counterelectrode is the platinum coil.Device is placed in the faraday cup to reduce electronic noise.
Be the SEM imaging, with the chromium layer of 5nm and 50nm and gold layer evaporation on a slice silicon wafer.Chip also cleans with sulfuric acid, and flame annealing and the ethanolic solution of putting into the MUA (Sigma-Aldrich) of 10mM are placed 10min.
B) preparation and printing
Using the pH value is the sodium radio-phosphate,P-32 solution (Nas of 7 concentration as 3.26mM
2HPO
4/ NaH
2PO
4) (Merck) prepare horse heart cyt c (Sigma-Aldrich) solution of 12.6 μ M as buffer.Dimethione (PDMS) (Sylgard184, Dow Coming) ink pad is immersed in this cyt c solution.After the 2h, die is put into this solution and be pressed in lightly and keep 2min on the ink pad.In a single day ink pad separates with die, immediately the die drying-free is just put into the cushioning liquid that comprises base material, to cover protein with thin wet film, so that die is being transferred to the physiological condition that maintenance is expected the alternative process from a kind of solution.Transfer time is less than 5s.After die being transferred in the solution that comprises base material, make the conformal 2min of contact of die and base material by applying soft finger pressure, so that protein is transferred on the Au base material of MUA modification from die.Cyt c fixing on MUASAM based on electrostatic interaction.
The acidic group of MUA is removed proton and is with negative electrical charge thus, and cyt c has positive net charge.Because the positive charge of lysine group is positioned at the side of cyt c, so cyt c orientation from the teeth outwards is always identical.Fig. 1 has shown the SEM image of the pattern that shifts.Four wide lines of 150nm are clearly separated by the wide gap of 150nm (right side).There is not molecule in the space between the line that shifts.Can't see any common defects of μ CP or the sagging or the diffusion of shortcoming such as molecular ink.
C) cyclic voltammetry is measured
Adopt cyclic voltammetry to measure the redox active that is impressed into the protein on the silicon/Sioxide wafer of Au/Cr coating with non-structured die.Protein with B) in identical mode impress.After moving on to protein transduction on the base material, base material is directly transferred in the measuring cell.Fig. 2 show according to original place of the present invention μ CP technology (" original place printing ") cyt c afterwards with at environmental condition (wherein cyt c on die drying) the cyt c (" under environmental condition, impressing ") of impression and the cyclic voltammetry curve that the cyt c (" the cyt c in the solution ") that adsorbs from solution compares down.Under all scenario, all at E
0A clear and reversible redox peak appears in the redox potential place of=-60mV.The symmetry at peak show that cyt c is adsorbed to the surface.With suitable by original place printing and absorption prepare from solution sample, and the electric current of the protein of the transfer that observes under environmental condition is little by 70% at the electric current at redox potential place.This may be to cause owing to funtion part loss that lower protein density or dry run cause.
As if an importance of technology be that die is exposed to cushioning liquid and with base material does not take place the conformal duration that contacts.Fig. 3 has shown that the protein that shifts is exposed to cushioning liquid 5s-120min (5s, 10min and 2h) transfer process redox active before afterwards at die.It is long more that die is exposed to time of cushioning liquid, and the electric current under redox potential is low more.The reduction of electric current is caused by the decline of the surface coverage on the die.Because protein is just by being adsorbed on a little less than the London forces on the stamp surfaces, concentration gradient is ordered about the protein desorption in cushioning liquid.
The method according to this invention allows by adopting original place technology that the biomolecule patterning is also kept their structural intergrity and function simultaneously to little size to 150nm.
Disclosed feature of the present invention promptly can make up arbitrarily with it again separately and be used for implementing the present invention with its various forms in specification, claims and/or accompanying drawing.
List of references:
1.Xia,Y;Whitesides,G.M.;Annu.Rev.Mater.Sci.28(1998),153-184.
2.Michel, people such as B., IBM J.Res.﹠amp; Dev.45 (2001), 697-719.
3.Delamarche, people such as E.; J.Phys.Chem.B 102 (1998), 3324-3334.
4.Delamarche, people such as E.; J.Am.Chem.Soc.124 (2002), 3834-3835.
5.Bernard,A.;Delamarche,E.;Schmid,H.;Michel,B.;Bosshard,H.R.;Biebuyck,H.Langmuir?1998,14,2225-2229.
6.James,C.D.;Davis,R.C.;Kam,L.;Craighead,H.G.;Isaacson,M.,Turner,J.N.;Shain,W.Langmuir?1998,14,741-744.
7.Bernard,A.;Renault,J.P.;Michel,B.;Bosshard,H.R.;Delamarche,E.Adv.Mater.2000,12.1067-1070.
8.Lauer?L.;Ingebrandt?J.P.;Scholl?M.;Offenhauser?A.IEEE?Trans?Biomed?Eng?2001,48,83842.
9.Tarlov,M.J.;Bowden,E.F.J.Am.Chem.Soc.1991,113,1847-1849.
10.Song,S.;Clark,R.A.;Bowden,E.F,J,7.Phys.Chem.1993,97,6564-6572.
11.Clark,R.A.;Bowden,E.F.Langmuir?1997,13,559-565.
12.Runge,A.F.;Saavedra?S.S.Langmuir?2003,19,9418-9424
13.Nakao,H.;Gad,M.;Sugiyama,S.;Otobe,K.;Ohtani;T.J.Am.Chem.Soc.2003,125,7162.
Claims (30)
1. method of utilizing micro-contact printing process patterning molecule on substrate, by this method make will patterning molecule in whole micro-contact printing process process, be maintained in the solvent or and cover by solvent.
2. there is not drying steps according to the process of claim 1 wherein in the described micro-contact-printing.
3. the method for any one in requiring according to aforesaid right may further comprise the steps:
A) be provided in the solvent will patterning molecule and the surface of patterning is provided, the surface of die form preferably,
B) when described molecule being remained in the described solvent or being covered by described solvent, the molecular transfer of described desirable patternization is fixed thereon to the surface of described patterning and with them,
C) provide base material, and make the surface of described patterning conformal the contact be taken place with described base material with described molecule fixed thereon, thereby on described base material, set up the pattern of described molecule, described molecule is remained in the described solvent or by described solvent cover simultaneously.
4. according to the method for claim 3, wherein in step a), described molecule is provided in described solvent and at first is fixed on the ink pad that is positioned at the form on the surface of patterning not of being preferably within the described solvent.
5. according to the method for claim 4, wherein in step b), make described ink pad with the described molecule that is fixed thereon and described patterned surface in first solvent environment that contains described molecule that will patterning, described solvent and buffer randomly, conformal the contact be taken place, thus described molecular transfer is fixed thereon to the surperficial of described patterning and with them.
6. according to the method for claim 5, wherein in step c), containing described solvent and randomly providing described base material in second solvent environment of buffer, and the described patterned surface that wherein has a described molecule that is fixed thereon is transferred to after step b) in described second solvent environment and with described base material conformal the contact taken place.
7. according to the method for claim 4, wherein in step b), the described ink pad that will have the described molecule that is fixed thereon transfer to contain described solvent and randomly in second solvent environment of buffer after, make described ink pad conformal the contact be taken place in described second solvent environment, thereby described molecular transfer is fixed thereon to the surface of described patterning and with them with described patterned surface with the described molecule that is fixed thereon.
8. according to the method for claim 7, wherein in step c), containing described solvent and randomly providing described base material in the 3rd solvent environment of buffer, and the described patterned surface that wherein has a described molecule that is fixed thereon is transferred to after step b) in described the 3rd solvent environment and with described base material conformal the contact taken place.
9. according to the method for claim 3, wherein in step a), in described solvent, provide described molecule, and wherein in step b), within the described solvent described molecule is being fixed on the described patterned surface.
10. according to the method for claim 9, wherein step b) takes place by described patterned surface is immersed in the described solvent.
11. method according to claim 10, wherein in step c), containing described solvent and randomly providing described base material in the 4th solvent environment of buffer, and the described patterned surface that wherein has a described molecule that is fixed thereon is transferred to after step b) in described the 4th solvent environment and with described base material conformal the contact taken place.
12. method according to claim 3, wherein in step c), need not solvent environment and described base material is provided, and wherein when keeping described molecule to be covered by described solvent, make described patterned surface conformal the contact be taken place with described base material with the described molecule that is fixed thereon, and wherein with when described base material contacts, described patterned surface is transferred to and contains described solvent and randomly in the 5th solvent environment of buffer, described patterned surface takes place after making described patterned surface and described base material takes place by conformal the contact immediately with the transfer of described base material, and is dry on described base material to avoid described patterned surface.
13. according to any one method among the claim 3-12, the conformal molecule that occurs in described desirable patternization that contacts of described patterned surface and described base material is fixed on the described patterned surface afterwards no longer than 180min, preferably no longer than 120min, more preferably no longer than 10min, most preferably in the time period no longer than 1min.
14. according to any one method among the claim 3-13, wherein after step c), described patterned surface is mentioned from described base material, thereby stays the base material of the pattern that has described molecule on it.
15. according to the method for claim 14, the described base material that wherein has the molecule pattern on it is maintained in the solvent that randomly contains buffer or by its covering.
16. the method for any one in requiring according to aforesaid right, the molecule of wherein said desirable patternization is selected from protein, nucleic acid, preferred DNA or RNA, lipid, and the combination of above-mentioned substance.
17. according to the method for claim 16, the described molecule that wherein will be patterned is a protein molecule.
18. the method for any one in requiring according to aforesaid right, wherein, the molecule in desirable patternization described in the whole micro-contact printing process process covers, so they all keep its function and/or activity and/or native conformation in whole technical process owing to all being maintained in the solvent or by solvent.
19. according to the method for claim 18, the molecule of wherein said desirable patternization all is maintained in whole micro-contact printing process process under the physiological condition of being measured by for example pH and salinity.
20. the method for any one in requiring according to aforesaid right, wherein said base material comprises the separation layer and/or the adhesive layer that can promote described base material to pass through covalent bond, electrostatic force, Van der Waals force, hydrogen bond, London forces or their any combination and combine with the molecule of described desirable patternization.
21. the method for any one in requiring according to aforesaid right, wherein said base material is selected from metal and semimetal, monocrystalline or polycrystalline material; Preferably monocrystalline or polycrystalline metal and semimetal (most preferably gold, platinum, silicon); Or composite, preferably monocrystalline or polycrystalline composite materials (silica most preferably, GaAs) or amorphous state composite (most preferably glass); Plastics, elastomer (most preferably dimethyl silicone polymer) preferably, preferred plastic body (most preferably polyolefin), preferably ionomer, anticorrosive additive material (most preferably UV-NIL resist) preferably; With direct combination or any above-mentioned material of combination indirectly, the SAM that is used for indirect combination will have one or more chemicals or handle to realize the binding site of expectation with molecular layer, preferred SAM (self assembled monolayer) modification; The SAM that most preferably has two end groups: end group is used for molecule attached to base material, as is used for the mercaptan headgroup of combination on gold; The SAM that most preferably has the silane headgroup end group that is used to be combined on the silica; Second end group is used for the coupling ink, for example have the sulfydryl or the amino SAM that are used in conjunction with metal, SAM with the carboxyl that is used for the static combination, most preferably have the sulfydryl that is used in conjunction with metal, have band be used for the interactional methylene of Van der Waals level and smooth alkane chain, have be used for covalently bound-COOH ,-SAM of OH or vinyl; Or have the SAM that is used in conjunction with the antibody of corresponding antigens, or have the SAM that is used in conjunction with the antigen of corresponding antibodies, or have the SAM of the acceptor that is used for the specific bond molecule; And have be used in conjunction with the molecular layer modification of the antibody of corresponding antigens or with have be used in conjunction with the molecular layer modification of the antigen of corresponding antibodies or with any above-mentioned material of the molecular layer modification that has the acceptor that is used for the specific bond molecule; Most preferably use the gold of sulfydryl hendecanoic acid layer (MUA) modification.
22. according to any one method among the claim 3-21, wherein said patterned surface is made by being selected from following material: monocrystalline and polycrystalline material such as silicon, silica, the silica on laminar composite system such as the silicon, the metal level on the silicon/oxidative silicon; Amorphous material such as glass; Plastics, as elastomer, dimethyl silicone polymer preferably, plastic body, polyolefin (POP, polyolefin plastomers) preferably, ionomer, anticorrosive additive material such as UV-NIL resist.
23. according to any one method among the claim 3-22, wherein said ink pad, preferably make by being selected from following material: monocrystalline and polycrystalline material such as silicon, silica on the surface of described at least ink pad, silica on laminar composite system such as the silicon, the metal level on the silicon/oxidative silicon; Amorphous material such as glass; Plastics, as elastomer, dimethyl silicone polymer preferably, plastic body, polyolefin (POP, polyolefin plastomers) preferably, ionomer, anticorrosive additive material is as the UV-NIL resist.
24. according to any one method among the claim 3-23, the molecule of wherein said desirable patternization is selected from protein molecule such as redox protein matter, nucleic acid binding protein matter, enzyme, metalloprotein such as cytochrome c, azurin, cytoskeleton protein, antibody, nucleic acid such as DNA, RNA, PNA, lipid such as phosphatide and sphingolipid.
25. the method for any one in requiring according to aforesaid right, the molecule of wherein said desirable patternization is the protein molecule with one or several lysine residue, and wherein said base material is a gold, preferably have separation layer in its surface to avoid described protein denaturation, the thickness of described separation layer is preferably within the scope of 0.5nm-200nm.
26. the method for any one in requiring according to aforesaid right, wherein pattern comprise length for about 10nm to 500 μ m, preferably about 10nm arrives≤200nm, more preferably about 10nm arrives≤feature of 150nm.
27. also comprise the base material of the pattern of the molecule that can keep its function and/or activity and/or native conformation thereon by the method manufacturing of any one in requiring according to aforesaid right.
28. the application of base material according to claim 27 in sensor, bioreactor or cell guiding growth.
29. one kind is used for implementing any one the equipment of method of claim 1-26, comprises:
-hold desirable patternization molecule solution first the device,
The surface of-patterning, the surface of die form preferably,
-base material is maintained in the solvent or by solvent and covers,
-be used for that the molecule of described desirable patternization is transferred to second of described patterned surface from described first device to install,
-be used for the molecule of described desirable patternization is transferred to the 3rd device of described base material from described patterned surface,
-the molecule that is used for guaranteeing described desirable patternization is being transferred to the 4th device that described patterned surface is maintained at the solvent or is covered by solvent to the process of described base material again from described first device.
30. according to the equipment of claim 29, wherein said second device is an ink pad, the surface of preferred non-patterning.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05023880.7 | 2005-11-02 | ||
EP05023880A EP1782886A1 (en) | 2005-11-02 | 2005-11-02 | A method of patterning molecules on a substrate using a micro-contact printing process |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1958301A true CN1958301A (en) | 2007-05-09 |
CN1958301B CN1958301B (en) | 2010-06-23 |
Family
ID=36096436
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2006101436051A Expired - Fee Related CN1958301B (en) | 2005-11-02 | 2006-11-02 | A method of patterning molecules on a substrate using a micro-contact printing process |
Country Status (3)
Country | Link |
---|---|
US (3) | US7802517B2 (en) |
EP (1) | EP1782886A1 (en) |
CN (1) | CN1958301B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104246062A (en) * | 2012-03-19 | 2014-12-24 | 尼纳纸业公司 | Kits and methods of treating a substrate prior to formation of an image thereon |
CN105502281A (en) * | 2014-10-09 | 2016-04-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal patterning method |
CN111526990A (en) * | 2017-12-29 | 2020-08-11 | 3M创新有限公司 | Non-planar patterned nanostructured surfaces and printing methods for their fabrication |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0701909D0 (en) * | 2007-01-31 | 2007-03-14 | Imp Innovations Ltd | Deposition Of Organic Layers |
GB2453766A (en) * | 2007-10-18 | 2009-04-22 | Novalia Ltd | Method of fabricating an electronic device |
US8293354B2 (en) * | 2008-04-09 | 2012-10-23 | The Regents Of The University Of Michigan | UV curable silsesquioxane resins for nanoprint lithography |
CN101477304B (en) | 2008-11-04 | 2011-08-17 | 南京大学 | Stamping method for copying high-resolution nano-structure on complicated shape surface |
US8541162B2 (en) | 2010-09-01 | 2013-09-24 | E I Du Pont De Nemours And Company | High resolution, solvent resistant, thin elastomeric printing plates |
US8563220B2 (en) | 2010-09-01 | 2013-10-22 | E I Du Pont De Nemours And Company | High resolution, solvent resistant, thin elastomeric printing plates |
WO2012057706A1 (en) * | 2010-10-25 | 2012-05-03 | Nanyang Technological University | Method for micropatterning a substrate and a patterned substrate formed thereof |
WO2015042464A1 (en) | 2013-09-19 | 2015-03-26 | University Of Washington Through Its Center For Commercialization | Affinity tags and processes for purifying and immobilizing proteins using same |
CN104030238B (en) * | 2014-06-12 | 2015-12-09 | 西安交通大学 | Microcontact printing realizes the preparation method of graphical ZnO nano thread array |
US10650312B2 (en) | 2016-11-16 | 2020-05-12 | Catalog Technologies, Inc. | Nucleic acid-based data storage |
US11763169B2 (en) | 2016-11-16 | 2023-09-19 | Catalog Technologies, Inc. | Systems for nucleic acid-based data storage |
AU2019236289A1 (en) | 2018-03-16 | 2020-10-08 | Catalog Technologies, Inc. | Chemical methods for nucleic acid-based data storage |
CA3100529A1 (en) | 2018-05-16 | 2019-11-21 | Catalog Technologies, Inc. | Compositions and methods for nucleic acid-based data storage |
WO2020227718A1 (en) | 2019-05-09 | 2020-11-12 | Catalog Technologies, Inc. | Data structures and operations for searching, computing, and indexing in dna-based data storage |
KR20220080172A (en) | 2019-10-11 | 2022-06-14 | 카탈로그 테크놀로지스, 인크. | Nucleic Acid Security and Authentication |
JP2023526017A (en) | 2020-05-11 | 2023-06-20 | カタログ テクノロジーズ, インコーポレイテッド | Programs and functions in DNA-based data storage |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6180239B1 (en) * | 1993-10-04 | 2001-01-30 | President And Fellows Of Harvard College | Microcontact printing on surfaces and derivative articles |
US6518168B1 (en) * | 1995-08-18 | 2003-02-11 | President And Fellows Of Harvard College | Self-assembled monolayer directed patterning of surfaces |
US5948621A (en) * | 1997-09-30 | 1999-09-07 | The United States Of America As Represented By The Secretary Of The Navy | Direct molecular patterning using a micro-stamp gel |
US6399295B1 (en) * | 1999-12-17 | 2002-06-04 | Kimberly-Clark Worldwide, Inc. | Use of wicking agent to eliminate wash steps for optical diffraction-based biosensors |
US20010055801A1 (en) * | 2000-02-22 | 2001-12-27 | Shiping Chen | Liquid arrays |
WO2001083827A1 (en) * | 2000-05-04 | 2001-11-08 | Yale University | High density protein arrays for screening of protein activity |
KR100377946B1 (en) * | 2000-07-15 | 2003-03-29 | 한국과학기술원 | A Process for Preparing Monolayer by Using Dendrimer |
US7771922B2 (en) * | 2002-05-03 | 2010-08-10 | Kimberly-Clark Worldwide, Inc. | Biomolecule diagnostic device |
AU2003300257A1 (en) * | 2002-05-21 | 2004-05-04 | Northwestern University | Peptide and protein arrays and direct-write lithographic printing of peptides and proteins |
US20040156988A1 (en) * | 2002-08-26 | 2004-08-12 | Mehenti Neville Z. | Selective and alignment-free molecular patterning of surfaces |
US7434512B2 (en) * | 2002-09-09 | 2008-10-14 | International Business Machines Corporation | Printing in a medium |
KR100523767B1 (en) * | 2003-06-12 | 2005-10-26 | 한국과학기술원 | Method for fabricating a nanopattern using self-assembly of supramolecules and UV etching |
CA2545482A1 (en) * | 2003-11-10 | 2005-05-26 | Platypus Technologies, Llc | Substrates, devices, and methods for cellular assays |
EP1697039A1 (en) * | 2003-12-16 | 2006-09-06 | Koninklijke Philips Electronics N.V. | Molecular stamp for printing biomolecules onto a substrate |
-
2005
- 2005-11-02 EP EP05023880A patent/EP1782886A1/en not_active Withdrawn
-
2006
- 2006-06-30 US US11/477,655 patent/US7802517B2/en not_active Expired - Fee Related
- 2006-11-02 CN CN2006101436051A patent/CN1958301B/en not_active Expired - Fee Related
-
2010
- 2010-08-05 US US12/850,771 patent/US20100298169A1/en not_active Abandoned
-
2013
- 2013-06-21 US US13/923,668 patent/US20130280501A1/en not_active Abandoned
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104246062A (en) * | 2012-03-19 | 2014-12-24 | 尼纳纸业公司 | Kits and methods of treating a substrate prior to formation of an image thereon |
TWI593567B (en) * | 2012-03-19 | 2017-08-01 | 里拿紙業有限公司 | Kits and methods of treating a substrate prior to formation of an image thereon |
CN105502281A (en) * | 2014-10-09 | 2016-04-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Metal patterning method |
CN105502281B (en) * | 2014-10-09 | 2017-06-13 | 中国科学院苏州纳米技术与纳米仿生研究所 | A kind of metal patternization method |
CN111526990A (en) * | 2017-12-29 | 2020-08-11 | 3M创新有限公司 | Non-planar patterned nanostructured surfaces and printing methods for their fabrication |
CN111526990B (en) * | 2017-12-29 | 2022-09-27 | 3M创新有限公司 | Non-planar patterned nanostructured surfaces and printing methods for their fabrication |
Also Published As
Publication number | Publication date |
---|---|
EP1782886A1 (en) | 2007-05-09 |
US20130280501A1 (en) | 2013-10-24 |
US20100298169A1 (en) | 2010-11-25 |
CN1958301B (en) | 2010-06-23 |
US7802517B2 (en) | 2010-09-28 |
US20070098899A1 (en) | 2007-05-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1958301A (en) | A method of patterning molecules on a substrate using a micro-contact printing process | |
Magliulo et al. | Printable and flexible electronics: From TFTs to bioelectronic devices | |
Casalini et al. | Self-assembled monolayers in organic electronics | |
Carlson et al. | Transfer printing techniques for materials assembly and micro/nanodevice fabrication | |
EP2285923B1 (en) | Method for assembling two surfaces, or one surface, with a molecule of interest | |
Delamarche et al. | Microcontact printing using poly (dimethylsiloxane) stamps hydrophilized by poly (ethylene oxide) silanes | |
EP2553714B1 (en) | Methods for transferring nanoparticles onto substrates and for patterning nanoparticle films. | |
CN102037407B (en) | Polymer pen lithography | |
Xiang et al. | Fabrication of self-assembled monolayers (SAMs) and inorganic micropattern on flexible polymer substrate | |
CN101627336A (en) | Method to form a pattern of functional material on a substrate using a stamp having a surface modifying material | |
Martin et al. | Fabrication and application of hydrogel stampers for physisorptive microcontact printing | |
EP3966539A1 (en) | Substrates comprising nanowires | |
WO2005001573A3 (en) | Adhesion method using gray-scale photolithography | |
Amato | Pyrolysed Carbon Scaffold for Bioelectrochemistry in Life Science | |
Nazari et al. | Molecular combing of DNA: Methods and applications | |
Costello et al. | Application of nanotechnology to control bacterial adhesion and patterning on material surfaces | |
Ma et al. | Assembly of nanomaterials through highly ordered self-assembled monolayers and peptide-organic hybrid conjugates as templates | |
Costello et al. | Exploiting additive and subtractive patterning for spatially controlled and robust bacterial co-cultures | |
EP2720806B1 (en) | Process for functionalizing a surface with an object or molecule of interest | |
US7709298B2 (en) | Selectively altering a predetermined portion or an external member in contact with the predetermined portion | |
Hong et al. | " Surface-programmed assembly" of nanotube/nanowire-based integrated devices | |
Wang | Biosensors Fabrication by Polydimethylsiloxane Stamping and Nanostructured Platinum for Construction of Improved Reference and Sensing Electrodes | |
Parthasarathy et al. | Spatially controlled assembly of nanomaterials at the nanoscale | |
FR2947544A1 (en) | FUNCTIONALIZATION OF CARBON, SILICON AND / OR GERMANIUM SURFACES HYBRID SP3 | |
Luo et al. | Microcontact printed diaphorase monolayer on glass characterized by atomic force microscopy and scanning electrochemical microscopy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
ASS | Succession or assignment of patent right |
Owner name: FORSCHUNGSZENTRUM JULICH GMBH |
|
C41 | Transfer of patent application or patent right or utility model | ||
TR01 | Transfer of patent right |
Effective date of registration: 20110808 Address after: German Cohen Co-patentee after: Forschungszentrum Julich GmbH Patentee after: Sony Int Europ GmbH Address before: German Cohen Patentee before: Sony Int Europ GmbH |
|
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100623 Termination date: 20151102 |
|
EXPY | Termination of patent right or utility model |